KR100273601B1 - Method of manufacturing inorganic pigment - Google Patents

Abstract

The present invention is composed of composite oxides of various elements, which are excellent in weather resistance and heat resistance, and are inorganic pigments having various color tones widely used in ceramic colorants, paints and synthetic resin colorants. A sufficiently developed composite oxide pigment can be obtained to achieve a simplification of the grinding process. In the manufacturing method of the inorganic pigment which mixes the oxide of the element which comprises a specific inorganic pigment, or the compound which becomes an oxide by heating in predetermined ratio, and calcinates the blending raw material, A blending raw material is grind | pulverized instead of the said mixing process. Dry treatment is carried out to give sufficient energy to cause the mechanochemical reaction to the blended raw material, and the raw material particles are joined to coexist in the proportion of the blended raw material.

Description

Method of manufacturing inorganic pigments

Background Art Conventionally, many methods have been adopted and have been proposed regarding the production method of inorganic pigments composed of composite oxides.

As a general manufacturing method, there is a method of producing a composite oxide by making an oxide containing an element constituting a specific inorganic pigment or an oxide compound by applying heat at a predetermined ratio, followed by a step of making a composite oxide and miniaturizing it.

However, in this manufacturing method, since the solid phase reaction during firing is a reaction starting at the contact point of the raw material particles, the desired solid phase reaction is likely to be uneven and incomplete, and the color tone of the obtained pigment is uneven. Therefore, in order to obtain a homogeneous and sufficiently colored pigment, it is necessary to make baking temperature higher than necessary and to make baking time long enough. As a result, energy costs are not only high, but coarsening of the sintered body by sintering progresses over time, and thus, there is a problem of requiring enormous mechanical energy.

Another method is to make the blended raw material ultra-fine by long-time wet mixing pulverization, and to improve the mixed state to be more homogeneous and then fire it. According to this method, the firing time can be shortened to some extent, but incorporation of impurities arising from abrasion of the grinding tank or the grinding medium during wet mixing grinding is unavoidable, and this phenomenon adversely affects the quality of the pigment obtained.

In addition, there is also a method of using a flux such as fluoride or chloride together for the purpose of lowering the firing temperature, but the staining is severe and the grain growth by sintering is remarkable.

In addition, there is a method using the coprecipitation method. For example, it is disclosed in Japanese Patent Laid-Open No. 3-8728. In this case, by adopting a method using a coprecipitation method, a more homogeneous pigment can be obtained, but the manufacturing process is complicated and it is one of the reasons for the increase in manufacturing cost.

An object of the present invention is to obtain an inorganic pigment composed of a complex oxide sufficiently homogeneous and sufficiently colored in a simple process.

It is another object of the present invention to obtain a homogeneous and sufficiently colored composite oxide pigment by low temperature and short time firing that does not cause excessive sintering of the fired product, thereby achieving a simplification of the grinding process.

It is another object of the present invention to establish a production method for obtaining a homogeneously sufficiently colored green inorganic pigment composed of oxides of titanium, cobalt, nickel and zinc at low temperature and short time firing.

Another object of the present invention is a homogeneous, consisting of a rutile structure in which one or two or more of the oxides of cobalt, chromium and nickel and one or two or more of the antimony, tungsten and niobium oxides are dissolved in titanium oxide. The present invention is to establish a production method for obtaining a yellow inorganic pigment sufficiently developed by low temperature and short time firing.

It is still another object of the present invention to establish a production method in which a cobalt blue pigment which is homogeneous, sufficiently colored and excellent in transparency is obtained by low temperature and short time firing.

The present invention relates to a method for producing inorganic pigments of various colors, which are composed of composite oxides of various elements, which have excellent weather resistance and heat resistance, and are widely used in colorants for ceramics, colorants for paints and synthetic resins, and the like.

1 shows the X-ray diffraction profile of the particle powder obtained by the complexing treatment of Example 1 of the present invention and the mixture obtained by the wet grinding treatment of Comparative Example 1. FIG.

Fig. 2 shows an electron micrograph in place of the drawing of the particle surface obtained by the compounding process of Example 1 of the present invention.

Fig. 3 shows an X-ray image (EDX surface analysis) showing the distribution of titanium element in the particles obtained by the complexing treatment in Example 1 of the present invention.

Fig. 4 shows an X-ray image (EDX surface analysis) showing the distribution of cobalt elements in the particles obtained by the complexing treatment in Example 1 of the present invention.

Fig. 5 shows an X-ray image (EDX surface analysis) showing the distribution of nickel elements in the particles obtained by the complexing treatment in Example 1 of the present invention.

Fig. 6 shows an X-ray (EDX surface analysis) showing the distribution of zinc elements in the particles obtained by the complexing treatment in Example 1 of the present invention.

Fig. 7 is a diagram schematically illustrating the form of the composite particle powder obtained by the complexing process of Example 1 of the present invention based on the result of EDX surface analysis and recording.

FIG. 8 is a diagram schematically illustrating the form of the mixture obtained by the wet grinding treatment of Comparative Example 1 based on the results of EDX analysis.

9 shows the X-ray diffraction profile of the particle powder obtained by the complexing treatment of Example 3 of the present invention and the mixture obtained by the mixing treatment of Comparative Example 2. FIG.

Fig. 10 shows an electron micrograph in place of the drawing of the particle surface obtained by the compounding process of Example 3 of the present invention.

Fig. 11 shows an X-ray image (EDX surface analysis) showing the distribution of titanium element in the particles obtained by the complexing treatment in Example 3 of the present invention.

Fig. 12 shows an X-ray image (EDX surface analysis) showing the distribution of cobalt elements in the particles obtained by the complexing treatment in Example 3 of the present invention.

Fig. 13 shows an X-ray image (EDX surface analysis) showing the distribution of antimony element in the particles obtained by the complexing treatment in Example 3 of the present invention.

Fig. 14 is a diagram schematically illustrating and recording the form of the composite particle powder obtained by the complexing process of Example 3 of the present invention based on the EDX surface analysis results.

FIG. 15: is the figure which modeled and recorded the form of the mixture obtained by the mixing process of the comparative example 2 based on the EDX surface analysis result.

FIG. 16 is a diagram schematically illustrating the shape of the particle powder before the complexing treatment in Example 6 of the present invention based on the results of EDX surface analysis. FIG.

FIG. 17 is a diagram schematically illustrating the shape of the composite particle powder obtained by the complexing process of Example 6 of the present invention according to the result of EDX plane analysis. FIG.

Fig. 18 shows the X-ray diffraction profile of the particle powder before the compounding treatment in Example 6 of the present invention.

Fig. 19 shows the X-ray diffraction profile of the particle powder obtained by the compounding process of Example 6 of the present invention.

20 shows the X-ray diffraction profile of the cobalt blue pigment obtained in Example 6 of the present invention.

FIG. 21 is a diagram schematically illustrating the form of the mixture obtained by the wet mixed pulverization treatment of Comparative Example 4 based on the result of EDX analysis.

Fig. 22 shows the X-ray diffraction profile of the cobalt blue pigment obtained in Comparative Example 4.

The present invention provides a method for producing an inorganic pigment in which an oxide of an element constituting a specific inorganic pigment or a compound which becomes an oxide by applying heat at a predetermined ratio and calcinates the blended raw material is substituted for the electric mixing step. And dry blending the blended raw material with a grinder to provide sufficient energy to cause the mechanochemical reaction to the blended raw material, thereby joining the raw material particles to coexist in the proportion of the blended raw material.

By this mechanochemical reaction, raw material particles are strongly and firmly bonded, and at the same time, amorphous (amorphous) crystallization proceeds on the surface of the raw material particles. In addition, since this process causes pulverization at the same time as the compounding phenomenon, it also has the effect of preventing the increase in the diameter of the composite particles.

The particles obtained by the complexing treatment are composite particles in which each element constituting a particular inorganic pigment in which the particles are firmly bonded is coexisted in the proportion of the blended raw material, and is a composite particle that has undergone a change to amorphous, which is more reactive than crystalline. . In short, the above treatment results in a significant increase in the contact point, that is, the reaction point, between particles, which are important factors for the solid phase reaction rate, and the amorphousization of the composite particles, which contributes to further reaction reaction. No firing is required. Therefore, it is possible to obtain a homogeneous and sufficiently colored inorganic pigment under the firing conditions in which sintering does not proceed.

The effects and phenomena caused by the mechanochemical reactions are characterized by the progress of the amorphous phase in the X-ray diffraction results, the exotherm in the thermal analysis such as TG-DTA / DSC, the disappearance or shift of the endothermic peak, and the reduction of the specific surface area due to the complexation This can be confirmed by transition to a trend.

This mechanochemical reaction itself is well known, and it is known that it can adapt to the surface modification of powders, the formation of high-temperature superconducting materials, etc., but it is a green inorganic pigment composed of a complex oxide of a spinel structure composed of elemental oxides of titanium, cobalt, nickel and zinc. There is no example applied to the manufacturing method of inorganic pigments, including, and it is not known at all what the obtained inorganic pigments have.

As a starting material for the present invention, any oxide containing an element constituting a specific inorganic pigment or a compound which becomes an oxide by applying heat can be used. Particularly, starting materials applied to green inorganic pigments may be cobalt hydroxide or nickel as a cobalt source. A combination of nickel carbonates as a source may be used to facilitate amorphousization with lower energy addition.

Among the starting materials applied to the rutile yellow inorganic pigment, a combination of cobalt hydroxide in cobalt source, chromium hydroxide in chromium source and nickel carbonate in nickel source can easily proceed to amorphization with lower energy addition. .

In the production of cobalt blue pigments, a pigment having excellent transparency can be obtained by using cobalt hydroxide or cobalt carbonate as a cobalt source and aluminum hydroxide or gamma -alumina as an aluminum source.

There is no restriction | limiting in particular in the grinding | pulverizer used for complexing starting material powder. For example, an electric ball mill, a vibration mill, a stone mill mill, an impact mill, a roll electric mill, a disk mill, a pin mill, a media stirring mill, a planetary ball mill, etc. are mentioned. However, it is preferable to include a grinding mechanism by grinding, such as a vibration mill, a media stirring mill, a planetary ball mill, etc. in that it is easy to induce a mechanochemical reaction. In addition, in the case of a mill using a grinding media, the grinding media can be used for any of rods, cylinders, and balls, but is preferably subjected to compounding under conditions in which the grinding effect is increased. For example, in the case of a vibration mill or a planetary ball mill, the grinding effect can be easily increased by using 1.1 to 2.0 times the diameter of the ball suitable for fine grinding, or by using the ball in an increase of 1-2%.

In addition, in the compounding treatment, it is effective to add a small amount of liquid preparation to prevent adhesion to the pulverizing medium. For example, ethanol and propanol, which are widely used as dry grinding aids, are preferable. In the addition amount, addition in the range of 0.05 to 5.0 weight% is preferable with respect to the total amount of blending raw materials.

At the time of the compounding treatment, as an agent for causing the bonding between particles with lower energy, an organic substance having a sufficient viscosity to be adsorbed on the surface of the inorganic substance as a raw material and to serve as a binder is particularly effective. For example, organic substances having several hydroxyl groups or carboxyl groups in l molecules in terms of adsorption to inorganic surfaces, specifically polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin, alcohol amines such as diethanolamine and triethanolamine, or one molecule Dicarboxylic acid which has several carboxyl groups, polycarboxylic acid, etc. are mentioned in this. If the organic material is solid or excessively high viscosity at room temperature, a solution in which water or other solvent has a viscosity of 10 centipoise to 500 centipoise is used. It is a viscosity of the range suitable for uniformly disperse | distributing to the whole raw material particle. The addition amount is in the range of 0.05% by weight to 5.0% by weight, preferably in the range of 0.5% by weight to 2.0% by weight relative to the total amount of the blended raw materials. For example, if the addition amount is more than 5.0% by weight, most of the raw materials are attached untreated to the inner wall of the grinding tank or the grinding medium in the initial stage of the compounding treatment, and the deposits inhibit the subsequent processing and the addition effect is less than 0.05% by weight. Is hardly recognized. The use of this preparation improves the processing efficiency, and in some cases, the treatment can be performed within a time sufficient for practical use even in a low energy type grinder that requires a long time complexation treatment.

Examples 1 to 2 below show examples of applying the present invention to the production of green inorganic pigments.

Example 1

100 g of metatitanic acid was combined to make 48.3 g of cobalt hydroxide, 135.8 g of nickel carbonate, and 42.2 g of zinc oxide, and the mixture was subjected to dry treatment for 2 hours by using a vibration ball mill (MB-1 type / Centralized Air Co., Ltd.). . At this time, a container was used as a nylon pot (3.0 L), and the grinding medium used was 25 kg of alumina ball 5.0 kg, and the input amount of the blended raw material was 100 g.

1 is an X-ray diffraction profile of particle powder obtained by the above treatment using an X-ray diffraction apparatus (RADШ / Science Electric Co., Ltd.). From this, it was recognized that the blended raw material was a particle powder in which amorphousization proceeded remarkably.

Fig. 2 is an electron micrograph (S-2300 type scanning electron microscope, Hitachi, Ltd.), and it was observed that a plurality of raw material particles were firmly bonded to form secondary particles grown tens of times.

3 to 6 are X-ray images showing the distribution state of each metal element of titanium, cobalt, nickel and zinc obtained by EDX surface analysis (energy dispersive X-ray microanalyzer EMAX-3700 / Horiba Corporation). to be. It was found from these that the secondary particles were composite particles in which all of the elements of titanium, cobalt, nickel and zinc coexisted.

Therefore, by carrying out the compounding treatment of the present invention on the blended raw material, it was possible to obtain composite particles containing all metal elements contained in the blended raw material, in which the particles having undergone amorphization were firmly bonded to each other. FIG. 7: is the figure which recorded typically the form of the said composite grain | particle.

Subsequently, the composite powder obtained by calcination at 800 ° C. to 1100 ° C. in the air for 1 hour in a furnace was pulverized to 1 μm or less, followed by coloration and coloration. The order of color and measurement is as follows.

<Method of measurement>

Mayonnaise bottles (70 cc) were mixed in the following weight ratios and dispersed in a paint shaker (5400 type paint conditioner / red devil company) for 20 minutes.

4 g of sample (1 μm or less)

Glass Beads (Uni-Biz UB-2527L / Union) 45g

Acrylic resin (Nape Acrylic Auto Clear Super) 40g

Thinner 2g

The applicator was colored with an applicator (150 μm), measured with a spectrophotometer (Karacom Systems / Danich Purification Co., Ltd.), and compared and evaluated with a quartz cell colorimeter (HVC).

〈Modified Monochrome Colorimeter〉

The color wheel currently used as a display method of hue is represented by 40 kinds of 10 colors (R, YR, Y, GY, G ..) divided into 4 types. For example, from green to strong yellow to less yellow The value of H (color) is 7.5GY, 10GY, 2.5G, 5G over green. For example, green inorganic pigments are widely used in the range of 2.0G to 2.7G, and pigments having H (color) of 2.0G are used. A yellowish green pigment, on the other hand, a pigment with a H (color) of 2.7G is a green pigment with a strong green color.

In general, V (brightness) sets a value from 1 to 10, and the brightness increases as the value approaches 10. C (saturation) sets a value from 0 to 16, and the sharpness increases as the value increases.

Table 1 shows measurement results such as firing temperature, time, and H (color) using a quartz cell colorimeter.

Firing temperature (℃) Firing time (hours) No Tandem Marks Baked Tint (Night) Value by Corrected Munsell Color System H (color) V (brightness) C (saturation) Example 1 800 One radish Not enough color development - - - 850 One radish Vivid green coloration 2.41G 4.75 7.72 1050 One radish 2.65G 4.87 8.08 1100 One radish 2.27G 4.71 7.92 Comparative Example 1 900 4 U Not enough color development - - - 1000 4 U 〃 - - - 1050 One U Dull yellowish green coloration 1.05G 4.79 5.78 1050 4 Little u Yellowish green coloration 1.98G 4.72 7.68 1100 One U 〃 1.34G 4.74 6.66 1100 4 radish Vivid green coloration 2.24G 4.68 8.18

A pigment which was sufficiently colored by one hour firing at 800 ° C. was not obtained, but H (color) was 2.65 G at 2.41 G, which was very homogeneous under the firing conditions where firing was not performed at 850 ° C. to 1050 ° C. for one hour. A dark green pigment in between was obtained. When firing was carried out for 1 hour at 1100 ° C, a clear green color was obtained, but since the firing temperature was high, the sintering proceeded and the disintegration during the color transfer took a considerable time.

Comparative Example 1

As a comparative example, a blended raw material having the same composition as in Example 1 was subjected to wet mixed grinding in an electric ball mill (pot mill) and fired.

The wet mixed grinding at that time was performed on condition of the following. As a container, 2.0 liter nylon pot and 5 millimeter alumina ball 3.0 kg were used, 200 g of blended raw material and 0.8 liter of water were added, and the resultant slurry was continuously operated for 6 hours. The slurry was dried at 100 ° C. for 48 hours. It was.

As shown in the X-ray diffraction profile of FIG. 1, the mixture obtained by drying did not proceed with amorphous like the composite particle powder obtained in Example 1.

In addition, when the particle surface was observed with an electron microscope, the formation of secondary particles as shown in Example 1 was not recognized.

Fig. 8 is a schematic diagram of the EDX plane analysis results. Thus, a composite particle obtained by the treatment described in Example 1 which was a very fine mixture of primary particles could not be obtained.

Subsequently, the mixture was calcined at 900 to 1100 ° C. for 1 hour or 4 hours in an air in a roller hearth furnace, and the resulting calcined product was measured in the same manner as in Example 1.

Table 1 shows the results of measurement of the firing temperature, time, H (color) by using a quartz cell color system, and the like.

At any firing temperature, when the firing time was 1 hour, the burned material was noticeable and yellowish green. Firing conditions of 4 hours or more at 1050 ° C. are required to obtain a homogeneous and sufficiently colored fired product. In addition, the particles fired for 4 hours showed remarkable growth of particles due to sintering and required considerable time to disintegrate the sample.

Example 2

Dilute any one of ethanol, propylene glycol, polycarboxylic acid (dispalon 2150 / Kusmoto Chemical Co., Ltd.), triethanolamine, diethanolamine or monoethanolamine as it is or with ethanol to adjust to a predetermined viscosity and prepare it. It was set as (A)-(H). Subsequently, when 100 g of the same blending raw material as in Example 1 was added, these preparations (A) to (H) were added simultaneously, and the complexing treatment described in Example 1 was performed. However, the treatment time is 0.5 hours to 2 hours, and the amount of preparation at that time is prepared by adding (A) to (H) to 1% by weight of the total amount and adding 10% by weight of preparation (H) to preparation (H '). I did it.

Subsequently, each composite grain powder obtained by the above treatment was calcined at 850 ° C. for 1 hour in an air in a roller hearth furnace, and the color development degree of each calcined product was compared and evaluated based on Example 1 without addition of a preparation.

The component of the preparation (A)-(H ') added to Table 2, the viscosity (20 degreeC / centipoise), and the color development degree of the baked material in the said baking conditions were shown.

When the preparations (D) to (H) are added, that is, the viscosity of the preparation is in the range of 10 centipoise to 500 centipoise, and a preparation containing an organic substance having a hydroxyl group or a carboxyl group or two or more thereof in one molecule is added. In this case, an effect equivalent to the treatment described in Example 1 was recognized by the compounding treatment for 1 hour or 1.5 hours. Therefore, by adding the preparations (D) to (H), the present invention can be treated in a shorter time, i.e., with a lower energy addition, than in the case of Example 1 without the preparation. However, about the preparation (A), (B), (C), the remarkable effect similar to the preparation (D)-(H) was not recognized. This is a solution containing an organic substance having only one hydroxyl group in one molecule, such as the preparation (A) and (C). The adsorbing force on the surface of the preparation lacks the adsorption force and cannot act as a binder. Because they did not contribute directly. In addition, as in the preparation (B), even organic substances having two or more hydroxyl groups in one molecule did not directly contribute to the bonding between the particles without the viscosity required to act as a binder.

Moreover, (H ') which added 10 weight% of preparations (H), sufficient color development was not acquired even when the compounding process was performed for 2 hours. This is because the over-addition of the preparation caused the majority of raw materials to adhere untreated to the inner wall of the pot or to the alumina balls at the initial stage of the complexation treatment, and this deposit inhibited the subsequent treatment.

Hereinafter, Example 3 to Example 5 describe an example in which the present invention is applied to the production of a yellow inorganic pigment having a rutile structure.

Example 3

sample TiO ₂ 0.99TiO ₂ parts by weight Co (OH) ₂ 0.80 CoO parts by weight Cr (OH) ₃ 0.71 Cr ₂ O ₃ parts by weight NiCO ₃ 0.53 NiO parts by weight Sb ₂ O ₅ 0.91Sb ₂ O ₅ parts by weight WO ₃ parts by weight Nb ₂ O ₅ parts by weight One 79.9 1.5 6.3 2 79.9 1.5 7.7 3 79.9 1.5 4.7 4 79.9 1.5 3.2 3.9 5 79.9 1.5 3.2 2.4 6 79.9 1.5 3.9 2.4 7 79.9 1.5 2.1 2.6 1.6 8 79.9 7.2 17.6 9 79.9 4.1 7.0 10 79.9 2.8 2.1 14.3

In Table 3 showing the composition of the blended raw materials, the predetermined amount described in Sample 1 was combined and subjected to a compounding treatment by dry type for 3 hours using a vibration ball mill (MB-1 type / Centralized Air Co., Ltd.). At this time, a container was used as a nylon pot (3.0 L), and the grinding media used was 25 kg of alumina balls 5.0 kg, and the amount of the blended raw material was 100 g.

Fig. 9 is an X-ray diffraction profile of the particle powder obtained by the above treatment, from which it was recognized that amorphous powder of the blended raw material was advanced.

10 is an electron micrograph and it was observed that a plurality of raw material particles were firmly bonded to form secondary particles.

11 to 13 are X-rays showing the distribution states of the metal elements of titanium, cobalt and antimony obtained by EDX surface analysis. From these, the secondary particles were found to be composite particles in which all of the elements of titanium, cobalt and antimony coexist.

Therefore, by carrying out the compounding treatment of the present invention on the blended raw material, it was possible to obtain composite particles containing all metal elements contained in the blended raw material, in which the particles having undergone amorphization were firmly bonded.

14 is a diagram schematically showing the form of the composite powder.

Subsequently, the composite particle powder having the composition of Sample 1 was calcined for 1 hour at 800 ° C. to 11100 ° C. in an air in a roller hearth furnace or a SiC electric furnace, and the resulting fired product was colorized in the same manner as in Example 1. Colorimetric results were compared and evaluated using the CIELAB colorimeter.

Table 4 shows the firing temperature, time and colorimetric results by CIELAB colorimeter.

sample Firing temperature (℃) Firing time (hours) Baked Tint (Night) Value by CIELAB Colorimeter L * a * b * Example 3 One 800 1.0 Light reddish yellow 73.0 9.6 34.8 1000 1.0 Reddish yellow 70.7 13.4 40.8 1100 1.0 Dark reddish yellow 59.9 23.7 49.9 Comparative Example 2 One 800 1.0 Undeveloped - - - 1000 1.0 Light yellow 82.0 1.2 23.9 1100 1.0 Light reddish yellow 75.6 9.6 35.4 1100 6.0 Reddish yellow 70.5 13.9 42.3

By carrying out the complexing treatment, a uniform reddish yellow color development was observed under a firing condition of 800 ° C. for 1 hour. In the conventional manufacturing method, color development is not recognized at all under these firing conditions. Furthermore, the higher the temperature, the higher the color of the pigment obtained, the stronger the color is, and the reddish-yellow pigment having color development that cannot be obtained without firing at 1100 ° C. for 6 hours by firing at 1000 ° C. for 1 hour. Could get When calcined at 1100 ° C., although the same raw materials and the same composition were obtained, dark pigments of both yellow and red which could not be obtained even by firing for 6 hours or more in the conventional manufacturing method were obtained with a firing time of only 1 hour.

Comparative Example 2

The predetermined amount shown in the sample 1 of Table 3 was combined, and it mixed with the Henschel mixer (Sample Mill / Coarse Processing Co., Ltd.). As a result of investigating the crystal structure of Sample 1 after the mixing treatment with the X-ray diffractometer, as shown in FIG. 9, the amorphous treatment of the blended raw material was not recognized. When the particle surface was observed under an electron microscope, the formation of secondary particles as observed in Example 3 was not recognized. In addition, when the distribution state of each metal element was examined by EDX surface analysis, it was recognized that each element of titanium, cobalt, and antimony existed alone.

Therefore, the composite particle obtained by the process of Example 3 was not able to be obtained by the mixing process by the conventional manufacturing method.

Fig. 15 is a diagram schematically recording the form of the blended raw material after the mixing process.

Subsequently, the mixture having the composition of Sample 1 was calcined for 1 hour to 6 hours at 800 ° C. to 1100 ° C. in an air in a roller hearth or in a SiC electric furnace, and colorized in the same manner as in Example 3.

Table 4 shows the calcining effect according to the firing temperature, time and CIELAB color system.

The pigment obtained was noticeable when the firing time was 1 hour as compared with that of Example 3. In addition, the degree of color development was also lighter in both yellow and red colors as compared with the same firing conditions as in Example 3. In Example 3, baking was carried out at 1100 ° C. for 6 hours in order to develop colors up to a level obtainable at 1000 ° C. for 1 hour. I had to.

Example 4

The predetermined amounts described in Samples 2 to 10 in Table 3 were combined, and a compounding treatment was performed as in Example 3. Samples 2 to 10 after the complexing treatment were composite particles including all metal elements included in the blended raw material, in which the particles subjected to the amorphous process were firmly bonded as in the case of Example 3.

Subsequently, the composite particle powder having the composition described in Samples 2 to 10 was calcined for 1 hour at 1000 ° C. in an air in a roller hearth or an SiC electric furnace, and then colorated in the same manner as in Example 3.

Table 5 shows the composition and colorimetric results by CIELAB color system.

Sample No. Furtherance Baked Tint (Night) Value by CIELAB Colorimeter L * a * b * Example 3 One Co-Sb-Ti Reddish yellow 70.7 13.4 40.8 Example 4 2 Co-W-Ti 〃 68.7 12.9 40.1 3 Co-Nb-Ti 〃 71.9 13.0 41.2 4 Co- (Sb, W) -Ti 〃 70.5 13.2 40.4 5 Co- (Sb, Nb) -Ti 〃 72.1 13.3 39.7 6 Co- (W, Nb) -Ti 〃 70.4 13.1 40.2 7 Co- (Sb, W, Nb) -Ti 〃 71.7 13.2 39.2 8 Cr-Sb-Ti 〃 71.8 11.7 54.8 9 Ni-Sb-Ti Lemon Yellow 90.4 -11.5 48.4 10 (Co, Ni) -Sb-Ti Reddish yellow 65.1 12.7 46.9 Comparative Example 2 One Co-Sb-Ti Light yellow 82.0 1.2 23.9 Comparative Example 3 2 Co-W-Ti 〃 81.3 1.1 23.4 3 Co-Nb-Ti 〃 83.6 1.4 24.1 4 Co- (Sb, W) -Ti 〃 82.8 1.0 23.3 5 Co- (Sb, Nb) -Ti 〃 81.9 1.1 23.6 6 Co- (W, Nb) -Ti 〃 83.1 1.1 22.9 7 Co- (Sb, W, Nb) -Ti 〃 83.4 1.2 23.1 8 Cr-Sb-Ti Grayish greenish yellow 76.7 -5.8 40.5 9 Ni-Sb-Ti Light lemon yellow 91.8 -13.0 38.1 10 (Co, Ni) -Sb-Ti Light yellow 78.1 1.6 27.5 Firing condition: 1 hour at 1000 ℃

Any of Samples 2 to 7 could obtain a pigment having a very uniform reddish yellow color development. In other words, even when tungsten and niobium were used in place of antimony or in combination with a solid solution of rutile titanium oxide, the effect of the compounding treatment was recognized as in Example 3.

In addition, any of Samples 8 to 10 was able to obtain a pigment having a very uniform reddish yellow or lemon yellow color development. That is, even when chromium, nickel, and cobalt and nickel were dissolved in rutile titanium oxide instead of cobalt, the effect of the compounding treatment was recognized as in Example 3.

Comparative Example 3

Predetermined amounts described in Samples 2 to 10 in Table 3 were combined, and a mixing process was performed in the same manner as in Comparative Example 2. In any of Samples 2 to 10, the composite particles described in Example 3 could not be obtained by mixing, as in the case of Comparative Example 2.

Subsequently, the calcined product obtained by baking the mixture of the composition described in the sample 10 in the sample 2 with the roller hush or the SiC electric furnace at 1000 degreeC in air | atmosphere for 1 hour was measured like Example 3.

Table 5 shows the composition and colorimetric results by CIELAB color system.

As for the obtained pigment, staining was outstanding and color development was inadequate with respect to the composition of Example 4 in any of Samples 2-10.

Example 5

Either ethanol, propylene glycol, polycarboxylic acid (dispalon 2150 / Kusumoto Chemical Co., Ltd.), triethanolamine, diethanolamine or monoethanolamine as it is, or diluted with ethanol to adjust to a predetermined viscosity and they Was taken as preparation (A)-(H). Subsequently, these preparations (A)-(H) were added to 100 g of the mixing | blending raw materials of the composition of the sample 1 shown in Table 3, and the complexing process described in Example 3 was performed. However, the treatment time was 0.5 hours to 2 hours, and the amount of preparation added was 1% by weight of the total amount of the preparation (A) to (H), and 10% by weight of the preparation (H) was used as preparation (H '). .

Subsequently, each composite particle obtained by the above treatment was calcined at 800 ° C. for 1 hour in an air in a roller hearth furnace, and the degree of color development of each calcined product was evaluated.

The component of the preparation (A)-(H) added to Table 6, the viscosity (20 degreeC / centipoise), and the color development degree of the baked material in the said baking conditions were shown.

When preparation (D)-(H) is added, ie, the viscosity of preparation is in the range of 10 centipoise to 500 centipoise, and the preparation which contains the organic substance which has a hydroxyl group or a carboxyl group, or two or more in one molecule. When was added, the effect equivalent to the process described in Example 3 was recognized by the compounding process of 1 hour or 1.5 hours. Therefore, the treatment of the present invention was made possible by the addition of the preparations (D) to (H) in a shorter time, that is, the addition of less energy, than in the case of Example 3, in which the preparation was not added. However, in preparation (A), (B), and (C), the remarkable effect of the preparation (D)-(H) grade was not recognized. This solution contains organic matter that has only one hydroxyl group in one molecule such as preparation (A) and (C), and it does not function as a binder due to the lack of adsorption on the surface of the prepared inorganic material and contributes directly to the bonding between particles. Because you did not. Moreover, even if it is an organic substance which has two or more hydroxyl groups in 1 molecule like preparation (B), it did not directly contribute to the bonding between particle | grains, unless the viscosity required to act as a binder.

Moreover, (H ') which added 10 weight% of preparations (H), sufficient color development was not acquired even when the compounding process was performed for 2 hours. This is because the over-addition of the preparation caused the majority of the raw material to adhere untreated to the inner wall of the pot or to the alumina ball at the initial stage of the compounding treatment, and this deposit inhibited the subsequent treatment.

The following Example 6 and Example 7 show the example which applied this invention to manufacture of cobalt blue pigment.

Example 6

As a starting material, cobalt hydroxide and aluminum hydroxide were combined so that the molar number of cobalt was 0.30 with respect to 1 mol of aluminum, and the compounding treatment was carried out by a dry ball mill (MB-1 type / Centralized Air Co., Ltd.) for 3 hours in a dry manner. At this time, the container was used as a nylon pot (3.0 L), and the grinding media used was 5.0 kg of 25 mm aluminum balls, and the input amount of the compounding material was 200 g.

FIG. 16 and FIG. 17 are diagrams showing the distribution states of the cobalt and aluminum metal elements by EDX surface analysis of the blended raw materials before the treatment and after the treatment, and recording the results. Previously, it was found that the particle powder after the treatment was a composite particle in which cobalt and aluminum were uniformly distributed, which was a simple mixture of cobalt hydroxide particles and aluminum hydroxide particles.

FIG. 18 and FIG. 19 show that the compounding raw material was amorphized (crystallization of crystallization) by the compounding treatment as X-ray diffraction profiles of the blended raw material before the treatment and the particle powder after the treatment.

In other words, it was found that the composite particles obtained by the above treatment were composite particles in which cobalt hydroxide and aluminum hydroxide co-crystallized in a predetermined ratio coexist.

Subsequently, the composite powder was calcined at 950 ° C. for 30 minutes in an air in a roller hearth furnace, and a deep blue color developed. Since the obtained fired material was fired at a low temperature and for a short time, particle growth and significant sintering were not caused, and the particle size before and after firing was almost the same. After firing, dry grinding was performed immediately without performing wet grinding to obtain a cobalt blue pigment.

FIG. 20 shows an X-ray diffraction profile of the obtained pigment, from which it was found that all cobalt exists as a spinel-type composite oxide of cobalt aluminum, and the remaining aluminum exists as transition alumina having an amorphous low refractive index.

In addition, the cobalt blue pigment thus obtained was subjected to color development and coloration. The order of color and measurement is as follows.

<Method of measurement>

Mayonnaise bottle (70cc) was mixed in the following weight ratio and dispersed in a paint shaker (5400 type paint conditioner / Red Devils) for 15 minutes.

4 g of sample (1 μm or less)

Glass Beads (Uni-Biz UB-2527L / Union) 45g

Acrylic resin (nife creel auto clear super) 30g

Thinner 2g

Art paper with black bands was colored with an applicator (150 μm), colorimetrically measured with a spectrophotometer (Karacom Systems / Dainichi Chemical Co., Ltd.), and compared and evaluated with a CIELAB colorimeter.

<Evaluation method of colorimetric result>

The brightness is indicated by L *, and the chromaticity representing hue and saturation is indicated by a * and b *. a * and b * indicate the direction of color, + a * indicates the red direction, -a * indicates the green direction, + b * indicates the yellow direction, and -b * indicates the blue direction. Becomes The evaluation of the color itself uses the CIELAB colorimetric data of the white part of the art paper with black bands, and the transparency is measured by measuring L *, a *, b * of the white part of the art paper with black bands, respectively. Let bw, and then measure L *, a *, b * of the black part of the art paper with a black stripe, and set each as Lb, ab, bb. And these two color differences (DELTA) E were computed by the following formula, and it was set as the index of transparency. ΔE indicates that the larger the value, the greater the transparency.

When the colorimetric result of this pigment was expressed with the CIELAB color system, it was L * = 35.09, a * = 28.11, and b * =-68.57. Also, ΔE, an index of transparency, showed a high value of 53.43. This pigment was found to be a cobalt blue pigment having a bright reddish blue color because no cobalt oxide was present and only a spinel composite oxide of cobalt aluminum was present. In addition, since the remaining aluminum exists as transition alumina having a low amorphous refractive index, it has been found to have a feature of excellent transparency.

[Comparative Example 4]

As a starting material, cobalt hydroxide and aluminum hydroxide were combined so that the molar number of cobalt was 0.30 with respect to 1 mol of aluminum as in Example 6, and wet mixed grinding was performed in an electric ball mill (pot mill) under the following conditions. As a container, a slurry made of alumina pot (3.5 L) and a ground medium using 4 kg of 25 mm alumina ball, 200 g of mixed raw material and 1. l L of water were continuously operated for 24 hours in a wet manner, and dried at 110 ° C. .

FIG. 21 is a diagram schematically showing the results of EDX plane analysis of the obtained mixture, showing that each element of cobalt and aluminum does not exist as the same particle.

In addition, the X-ray diffraction profile of the mixture after the wet mixed pulverization, like the X-ray diffraction profile before the compounding treatment of Example 6, has a narrow peak width and strong intensity. From this, it was found that amorphousness of the starting material did not proceed.

This mixture did not develop blue color even when calcined under the same conditions as in Example 6. In order to develop a blue color, since baking needs to be 1200 degreeC or more, Preferably 1250 degreeC and about 3 hours, it baked at l250 degreeC for 3 hours. The resulting fired product had to be pulverized because sintering progressed and grain growth occurred. After wet grinding, it was dried and dried again to obtain a cobalt blue pigment.

Fig. 22 is an X-ray diffraction profile of the cobalt blue pigment thus obtained, in which the presence of a cobalt aluminum spinel-type composite oxide, cobalt oxide, and α-alumina was recognized. Cobalt found that a part became a spinel-type composite oxide of cobalt-aluminum, the remainder existed as cobalt oxide, and the remaining aluminum existed as α-alumina having high crystallinity and high refractive index.

This pigment colorimetric result was L * = 33.96, a * = 19.38, and b * =-59.83. In addition, ΔE, which is an index of transparency, showed a value of 28.26. Although this pigment is suitable for use as a blue pigment, in addition to the cobalt-aluminum spinel complex oxide, the firing temperature is too high compared to the pigment obtained in Example 6, and coexisting with α-alumina is greener than the pigment obtained in Example 6. It turned out to be a cobalt blue pigment which faded white and was inferior in transparency.

[Comparative Example 5]

The starting materials were combined under the same conditions as in Example 6, and the compounding treatment was performed under the same conditions.

Subsequently, the obtained composite powder was calcined at 800 ° C. for 2 hours to give a dark blue color development. This calcined product was calcined at low temperature and for a short time as in Example 6, so that no particle growth or significant sintering occurred, and the particle diameters before and after firing were almost the same. After firing, dry grinding was performed immediately without performing wet grinding to obtain a cobalt blue pigment. X-ray diffraction measurement was performed on the obtained pigment. The X-ray diffraction profile of this pigment showed a spinel-type composite oxide of cobalt-aluminum and an X-ray diffraction peak of cobalt oxide, but did not show an X-ray diffraction peak of alumina. Cobalt was found to be partly a spinel composite oxide of cobalt and aluminum, the remainder as cobalt oxide, and the remaining aluminum was present as transitional alumina with low amorphous refractive index.

When the colorimetric result of this pigment was shown by the CIELAB colorimetric system, L * = 24.21, a * = 10.39, and b * =-40.53. This pigment is not suitable for use as a blue pigment because cobalt oxide coexists in addition to the cobalt-aluminum spinel composite oxide and has a deep green color and lacks blue color as compared with the pigment obtained in Example 6. That is, it was found that at 800 ° C., the firing temperature was too low, resulting in poor color development, and at least 850 ° C. or higher was required to obtain a suitable color for use as a blue pigment.

Comparative Example 6

Starting materials were combined under the same conditions as in Example 6, and subjected to complexation under the same conditions. Subsequently, when the obtained composite particle powder was baked at 1100 degreeC for 30 minutes, it developed the color of dark blue. Since the fired material was fired in a short time, the particle growth and significant sintering were not caused, and the particle diameters before and after firing were almost the same. After firing, dry grinding was performed immediately without performing wet grinding to obtain a cobalt blue pigment.

X-ray diffraction measurement was performed on the obtained pigment. In the X-ray diffraction of this pigment, the X-ray diffraction peak of cobalt-aluminum spinel-type composite oxide and α-alumina was recognized in the flop, and the X-ray diffraction peak of cobalt oxide was not recognized. Cobalt was found to be all present as a spinel composite oxide of cobalt and aluminum, and the remaining aluminum was present as α-alumina having a high refractive index.

When the colorimetric result of this pigment was represented by CIELAB, it became U * = 33.14, a * = 20.18, and b * =-60.83. Also, ΔE, an index of transparency, showed a value of 36.68. This pigment is suitable for use as a blue pigment, but in addition to the cobalt-aluminum spinel composite oxide, the pigment has a high firing temperature compared to the pigment obtained in Example 6. It was found that it was a cobalt blue pigment.

Example 7

Cobalt carbonate and γ-alumina were used as starting materials, and the compounding treatment was conducted under the same conditions as in Example 6, with the molar number of cobalt being 0.30 per 1 mole of aluminum.

As a result of X-ray diffraction measurement, observation of particle surface by electron microscope and EDX surface analysis of the obtained particle powder, as in Example 6, a composite in which cobalt and aluminum undergoing an amorphous phase coexisted at a predetermined ratio It was found to be particles.

Subsequently, the composite powder was calcined at 950 ° C. for 30 minutes to give a dark blue color. Since the calcined product was calcined at low temperature and for a short time, no grain growth or significant sintering occurred, and the particle size before and after firing was almost the same. After firing, dry grinding was performed immediately without performing wet grinding to obtain a cobalt blue pigment.

X-ray diffraction measurement was performed on this pigment. In the X-ray diffraction profile of this pigment, only the X-ray diffraction peak of the cobalt-aluminum spinel-type composite oxide was recognized, but no cobalt oxide or α-alumina was recognized. That is, it was found that all of the cobalt reacted to exist as a spinel-type composite oxide of cobalt-aluminum, and the remaining aluminum existed as transitional alumina having low amorphous refractive index.

When the colorimetric result of this pigment was shown by the CIELAB colorimetric system, it was L * = 34.63, a * = 27.98, and b * =-67.40. Also, ΔE, an indicator of transparency, showed a high value of 52.64. It was found that this pigment was a bright blue dark blue cobalt blue pigment because cobalt oxide was not present and only a spinel composite oxide of cobalt aluminum was present. In addition, it was found that the remaining aluminum had excellent transparency because of the presence of transition alumina having a low amorphous refractive index.

Comparative Example 7

As starting materials, A) cobalt hydroxide, α-alumina, B) cobalt oxide, aluminum hydroxide, C) cobalt oxide, and α-alumina were respectively combined so that the molar number of cobalt was 0.30 per 1 mol of aluminum, and the same conditions as in Example 6 were used. The compounding process was performed.

As a result of X-ray diffraction measurement, observation of the particle surface by means of electron microscope and EDX surface analysis, the obtained particle powder is a composite in which cobalt and aluminium coexist with a predetermined ratio in a predetermined ratio as in Example 6. It was found to be particles.

Subsequently, when the composite powder was calcined at 950 ° C. for 30 minutes as in Example 6, all of A), B), and C) had a dark blue color, which was not suitable for use as a blue pigment. At 950 ° C, the firing temperature is too low, resulting in poor color development. Therefore, in order to obtain a color development suitable for use as a blue pigment, it is A) 1100 ° C, 2 hours, B) 1100 ° C, 1 hour, C Baking at 1150 ° C. for 2 hours was required. X-ray diffraction peaks of cobalt-aluminum spinel-type composite oxides, cobalt oxide, and α-alumina were recognized in the X-ray diffraction profiles of the pigments A) to C) obtained with sufficient color development. Cobalt was found to be partly a spinel-type composite oxide of cobalt and aluminum, the remainder as cobalt oxide, and the rest of aluminum as alpha-alumina with excellent crystallinity and high refractive index.

The colorimetric results of these pigments are shown in Table 7.

Cobalt One Aluminum Firing conditions Compound in pigment L * a * b * ΔE Example 6 Cobalt hydroxide Aluminum hydroxide 950 ° C / 30 minutes Composite Oxide, Transition Alumina 35.09 28.11 -68.57 53.43 Example 7 Basic cobalt carbonate γ-alumina 950 ° C / 30 minutes Composite Oxide, Transition Alumina 34.63 27.98 -67.4 52.64 Example 7A Cobalt hydroxide α-alumina 1100 ℃ / 2 hours Complex oxide, cobalt oxide, α-alumina 34.59 21.17 -57.64 35.52 Example 7B Cobalt oxide Aluminum hydroxide 1100 ℃ / 1 hour Complex oxide, cobalt oxide, α-alumina 32.66 19.38 -58.43 30.55 Example 7C Cobalt oxide α-alumina 1150 ℃ / 2 hours Complex oxide, cobalt oxide, α-alumina 33.28 29.51 -58.38 36.73

These pigments are suitable for use as blue pigments, but in addition to the cobalt-aluminum spinel composite oxide, the calcination temperature is too high compared to the pigment obtained in Example 6, and coexisting α-alumina due to coexistence with greenish-white color. It turned out that it is a blue pigment.

Claims (8)

Mixing the raw materials with sufficient energy to cause mechanochemical reaction by dry mixing the raw material mixture which mixed the oxide of two or more metal elements or the metal compound which becomes an oxide by a predetermined ratio by applying heat to a blending raw material Forming a composite particle in which a plurality of metal elements coexist, and firing the composite particle to synthesize a composite oxide. The method according to claim 1, wherein the metal elements are titanium, cobalt, nickel, and zinc, and the composite particles in which these elements coexist are calcined in a range of 850 to 1050 ° C to produce a green inorganic pigment. The method of claim 2, wherein titanium oxide or metatitanic acid is used as the titanium source, cobalt hydroxide is used as the cobalt source, and nickel carbonate is used as the nickel source. The method according to claim 1, wherein the metal element is an element selected from (a) titanium, (b) cobalt, chromium or nickel, and (c) an element selected from antimony, tungsten or niobium. Baking in the range of 800 to 1100 ℃ to produce a yellow inorganic pigment. The method according to claim 4, wherein cobalt hydroxide is used as cobalt source, nickel carbonate as nickel source, chromium hydroxide as chromium source, and titanium oxide or metatitanic acid as titanium source. The method according to claim 1, wherein the metal elements are cobalt and aluminum, and the composite particles in which these metal elements coexist are calcined in a range of 800 to 1050 ° C to produce a blue inorganic pigment. The method according to claim 6, wherein cobalt hydroxide or cobalt carbonate is used as the cobalt source, and aluminum hydroxide or γ-alumina is used as the compounding material as the aluminum source. The method according to any one of claims 1 to 7, wherein the forming of the composite particles comprises at least two hydroxyl groups in one molecule, at least two carboxyl groups in one molecule, or a sum of hydroxyl groups and carboxyl groups in one molecule. A method wherein the organic material having two or more is adjusted to a viscosity of 10 to 500 centipoise at room temperature (20 ° C.) is added in a range of 0.05% to 5.0% by weight of the total amount of the blended raw material.

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